Monoazo and disazo colorants

ABSTRACT

This invention relates to novel (N-substituted sulfonamido) monoazo and disazo compounds, to acid-addition salts of said azo compounds which are useful as direct dyes particularly in the dyeing of cellulose, to novel (N-substituted sulfonamido) substituted nitrobenzene, aniline and acetanilide intermediates to said azo compounds and to methods of preparation of said azo compounds and said intermediates to said azo compounds.

This application is a division, of application Ser. No. 195,128, filedOct. 8, 1980, now U.S. Pat. No. 4,376,729.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

This invention relates to a group of compounds classified in the fieldof chemistry and more particularly to novel monoazo and disazo compoundsuseful as direct dyes, particularly in the dyeing of cellulose; to theacid-addition salts thereof; to nitrobenzene, aniline and acetanilideintermediates thereto; and to processes for preparing said monoazo anddisazo compounds, said acid-addition salts and said nitrobenzene,aniline and acetanilide intermediates.

(b) Description of the Prior Art

A class of compounds known as direct dyes are known to be useful asdyeing agents for paper and fabrics. Among this group of direct dyesthere are water-soluble azo and disazo dyestuffs and their acid-additionsalts. However, heretofore known water-soluble azo and disazo dyestuffsand their acid-addition salts have suffered from a number ofdeficiencies when employed as dyes for coloring cellulose in the form ofbleached pulp of the type used for the manufacture of household papergoods such as paper napkins, paper toweling, facial tissues and soforth. Thus, they have been found to bleed undesirably out of paperproducts colored with them when the article is brought into contact withcommon household solutions, for example, water, milk, soap solutions,detergent solutions, alcoholic beverages, vinegar, rubbing alcohol, andso forth. They have also been found to have relatively poorsubstantivity to bleached pulp and suffer from a low rate and degree ofexhaust from dyeing solutions containing them. They have also been foundto have a relatively poor degree of color discharge when bleached withhypochlorite or "chlorine" bleach. There is thus a need for azodyestuffs for coloring bleached pulp which have a high bleed resistance,good substantivity, both a high rate and a high degree of exhaust fromaqueous dyeing solutions in which they are utilized, and which have ahigh degree of color discharge when bleached with hypochlorite or"chlorine" bleach.

The following items to date appear to constitute the most relevant priorart with regard to the instant invention.

U.S. Pat. No. 2,863,875 (issued Dec. 9, 1958) discloses azo dyestuffscontaining the radical [--SO₂ N--(R₁)(R₂ NR₃ R₄)]_(n) wherein R₁ ishydrogen or a lower alkyl, R₂ is a lower alkylene, R₃ and R₄ are loweralkyl or hydroxy lower alkyl, and n is one to eight. The products aretaught to be useful for dyeing cotton, wool, cellulose, polyamides,polyacrylics, paper and paper raw materials.

U.S. Pat. No. 3,096,322 (issued July 2, 1963) teaches monoazo dyestuffsand their precursor anilines and acetanilides bearing the radical --SO₂NHRN(R₁)₂ wherein R represents an alkylene radical having 2 or 3 carbonatoms and R₁ represents an alkyl radical having 1 to 4 carbon atoms orN(R₁)₂ collectively represents the heterocyclic piperidyl or morpholinylradicals. The azo compounds are taught to be useful for dyeing acrylicfibers.

French Pat. No. 1,253,766 (issued Apr. 11, 1960) teaches a monoazodyestuff bearing the radical ##STR1## wherein Y is a n alkylene and X isa 3 or 4 carbon alkylene. The azo compounds are taught to be useful whencomplexed with cobalt or chromium for dyeing wool, silk and polyamides.

SUMMARY OF THE INVENTION

In its composition of matter aspect, the invention relates to novel(N-substituted sulfonamido) monoazo and disazo compounds useful forcoloring natural fibers, synthetic fiber-forming material and cellulosicmaterials as well as in the manufacture of paper, varnishes, inks,coatings and plastics and to the acid-addition salt forms of the(N-substituted sulfonamido) monoazo and disazo compounds.

In another of its composition of matter aspects, the invention relatesto novel (N-substituted sulfonamido) substituted nitrobenzenes, anilinesand acetanilides.

In one of its process aspects, the invention relates to a process forpreparing the novel (N-substituted sulfonamido) monoazo and disazocompounds which comprises diazotizing an appropriate (N-substitutedsulfonamido) aniline and coupling the resulting diazonium salt with acoupling component.

In yet another of its process aspects, the invention relates to aprocess for preparing novel (N-substituted sulfonamido) monoazo anddisazo compounds which comprises in the first step reacting a monoazo ordisazo compound containing one or more sulfonic acid moieties withthionyl chloride to obtain a chlorosulfonyl monoazo or disazo compoundwhich is interacted in a second step with the appropriate diamine or(2-aminoethyl)-2-imidazolidinone.

In another of its process aspects, the invention relates to a processfor preparing the novel (N-substituted sulfonamido) substitutednitrobenzenes, anilines and acetanilides which comprises in a first stepchlorosulfonating a nitrobenzene or an acetanilide and in a second stepinteracting the chlorosulfonated nitrobenzene or acetanilide with theappropriate diamine or (2-aminoethyl)-2-imidazolidinone and if theaniline is desired, the acetyl moiety can be removed in an acidhydrolysis, or the nitro moiety can be reduced.

DETAILED DESCRIPTION INCLUSIVE OF THE PREFERRED EMBODIMENTS

More specifically, this invention in the first of its composition ofmatter aspects, relates to novel disazo compounds bearing (N-substitutedsulfonamido) groups said disazo compounds selected from the groupconsisting of ##STR2## R¹ represents a moiety selected from the groupconsisting of alkylene-NH-alkylene-NH₂, alkylene-N-(non-tertiary C₁ toC₄ alkyl)₂, ##STR3## and ##STR4## in which alkylene represents -CH₂CH₂ - and --CH₂ CH₂ CH₂ -- R², R³, R⁴ and R⁵ represent hydrogen, C₁ -C₃alkyl or C₁ -C₃ alkoxy; or the acid-addition salt forms of said disazocompounds.

In a first particular embodiment in accordance with the first of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) disazo compounds havingthe formula ##STR5## in which R¹ has the same respective meanings givenin Formula I.

In a second particular embodiment in accordance with the first of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) disazo compounds havingthe formula ##STR6## in which R¹ has the same respective meanings givenin Formula I.

In a third particular embodiment in accordance with the first of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) disazo compounds havingthe formula ##STR7## in which R¹ has the same respective meanings givenin Formula I.

In a fourth particular embodiment in accordance with the first of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) disazo compounds havingthe formula ##STR8## in which R¹ and R² each have the same respectivemeanings given in Formula IV.

In a fifth particular embodiment in accordance with the first of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) disazo compounds havingthe formula ##STR9## in which R¹ and R² each have the same respectivemeanings given in Formula V.

In a sixth particular embodiment in accordance with the first of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) disazo compounds havingthe formula ##STR10## in which R¹ and R³ each have the same respectivemeanings given in Formula VI.

In the second of its composition of matter aspects, the invention soughtto be patented resides in novel (N-substituted sulfonamido) monoazocompounds having the formula ##STR11## in which R¹ represents a moietyselected from the group consisting of alkylene-NH-alkylene-NH₂,alkylene-N-(non-tertiary C₁ to C₄ alkyl)₂, ##STR12## in which alkylenerepresents --CH₂ CH₂ -- and --CH₂ CH₂ CH₂ --;

R² represents hydrogen, C₁ to C₃ alkyl or C₁ to C₃ alkoxy;

R⁵ represents hydrogen or ##STR13## in which R⁰ represents hydrogen, C₁to C₃ alkoxy or C₁ to C₃ alkyl; or

the acid-addition salt forms of said monoazo compounds.

In a first particular embodiment in accordance with the second of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) monoazo compoundshaving the formula ##STR14## in which R¹, R² and R⁰ each have the samerespective meanings given in Formula VII.

In a second particular embodiment in accordance with the second of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) monoazo compoundshaving the formula ##STR15## in which R¹, R² and R⁰ each have the samerespective meanings given in Formula VII.

In a third particular embodiment in accordance with the second of itscomposition of matter aspects, the invention sought to be patentedresides in the novel (N-substituted sulfonamido) monoazo compoundshaving the formula ##STR16## in which R¹ and R² each have the samerespective meanings given in Formula VII.

In the third of its composition of matter aspects, the invention soughtto be patented resides in novel (N-substituted sulfonamido) anilines andacetanilides having the formula ##STR17## in which R^(1') represents-alkylene-NH-alkylene-NH₂ or ##STR18## in which alkylene represents--CH₂ CH₂ -- or --CH₂ CH₂ CH₂ --, R² represents hydrogen, C₁ to C₃alkoxy or C₁ to C₃ alkyl and R⁶ represents nitro, amino or acetamido; orthe acid-addition salt forms of said compounds.

In one of its process aspects, the invention sought to be patentedresides in the process for preparing (N-substituted sulfonamido) disazocompounds according to Formulas I, II and III which comprises in thefirst step interacting sulfonic acid substituted disazo compounds withchlorosulfonic acid and thionyl chloride to obtained chlorosulfonylsubstituted disazo compounds and in a second step, interacting thechlorosulfonyl-substituted disazo compounds obtained in step one with anexcess of an amine of the formula H₂ NR¹ to obtain the (N-sulfonamido)substituted disazo compounds wherein R¹ has the same respective meaningsgiven in relation to Formulas I, II and III.

In a second of its process aspects, the invention sought to be patentedresides in the process for preparing (N-substituted sulfonamido) disazocompounds according to Formulas IV and V which comprises in a first stepdiazotizing the appropriate (N-substituted sulfonamido)-R² -aniline anda second step two molecular proportions of the diazotized aniline arecoupled with one molecular proportion of a coupling component wherein R¹and R² each have the same respective meanings given in Formulas IV andV.

In a third of its process aspects, the invention sought to be patentedresides in the process for preparing (N-substituted sulfonamido) disazocompounds according to Formula VI which comprises in a first step,diazotizing a known azo compound (aminobenzenesulfonic acid-R³ -aniline)and coupling the diazonium salt with approximately one molecularproportion of a coupling component, a 2-hydroxynaphthalenesulfonic acid;in a second step, interacting the disazo compound thus formed withchlorosulfonic acid and thionyl chloride; in a third step, interactingthe resulting (chlorosulfonated) disazo compound with an excess of amineof the formula H₂ NR¹ ; and in a fourth step, isolating the resultingmixture of (N-R¹ -sulfonamido) disazo compounds.

In a fourth of its process aspects, the invention sought to be patentedresides in the process for preparing a (N-substituted sulfonamido)monoazo compound according to Formula VII which comprises in a firststep diazotizing a (N-substituted sulfonamido) aniline of the formula##STR19## and coupling the resulting diazonium salt with approximatelyone molecular equivalent of a coupling component of the formula##STR20## to obtain the corresponding (N-substituted sulfonamido)monoazo compounds in which R¹, R², R⁵ and x each have the samerespective meanings given in Formula VII.

In a fifth of its process aspects, the invention sought to be patentedresides in the process for preparing aN-[2-(2-oxo-imidazolidin-1-yl)sulfonamido]-R² -nitrobenzene according toFormula XI in which R^(1') representsN-[2-(2-oxo-imidazolidin-1-yl)ethyl] and R⁶ represents nitro whichcomprises interacting a R² -nitrobenzene sulfonyl chloride with anexcess 1-(2-aminoethyl)-2-imidazolidinone in the presence of pyridinewherein R² has the same meanings given in relation to Formula XI.

In a sixth of its process aspects, the invention sought to be patentedin the process for preparing aN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R² -aniline according toFormula XI in which R^(1') representsN-[2-(2-oxo-imidazolidin-1-yl)ethyl] and R⁶ represents amino whichcomprises reducing the correspondingN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R² -nitrobenzene whereinR² has the same respective meanings given in Formula XI.

In a seventh of its process aspects, the invention sought to be patentedresides in the process for preparing aN-[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido-R² -anilines according toFormula XI wherein R^(1') represents N-[N'-(2-aminoethyl)-2-aminoethyl]and R⁶ represents amino which comprises in a first step hydrolyzing thecorresponding N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R²-aniline in a strong acidic medium and in a second step rendering theresulting mixture from the first step alkaline wherein R² has the samerespective meanings given in Formula XI.

In an eighth of its process aspects, the invention sought to be patentedresides in the process for preparingN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R² -acetanilidesaccording to Formula XI wherein R^(1') representsN-[2-(2-oxo-imidazolidin-1-yl)ethyl] and R⁶ represents acetamido whichcomprises interacting the corresponding R² -acetanilide sulfonylchloride with 1-(2-aminoethyl)-2-imidazolidinone in the presence of analkali metal carbonate and pyridine wherein R² has the same respectivemeanings given in Formula XI.

In a ninth of its process aspects, the invention sought to be patentedresides in the process for preparingN-[N'-2-aminoethyl)-2-aminoethyl]sulfonamido-R² -anilines according toFormula XI in which R^(1') represents N-[N'-(2-aminoethyl)-2-aminoethyl]and R⁶ represents amino which comprises in a first step hydrolyzing thecorresponding N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R²-acetanilide in a strong acidic medium and in a second step renderingthe resulting mixture from the first step wherein R² has the samemeanings given in relation to Formula XI.

As used herein the term "C₁ to C₃ alkyl" and "C₁ to C₄ non-tertiaryalkyl" denotes saturated monovalent straight and branched aliphatichydrocarbon radicals including methyl, ethyl, propyl, isopropyl, butyl,secondary butyl and isobutyl.

The term "C₁ to C₃ alkoxy" includes saturated, acylic, straight orbranch-chained groups such as methoxy, ethoxy, propoxy and isopropoxy.

The term "acid-addition salt" is used herein to mean that the respectiveacid molecules are present in the dyestuff molecule in the form of acidaddition adducts. It will, of course, be understood that the precisetype of bonding will depend on the condition in which the dyestuffmolecule exists, that is, as a discrete solid or dissolved in solution.Thus, in the former, it would be expected that the acidic materialswould be bound by quaternization of primary, secondary and tertiaryamino substituents of the aminoalkylenesulfonamido tail chains while inthe latter, it would be expected although the aminoalkylenesulfonamidosubstituents would also be predominantly in the quaternized form, somedissociation is possible in such an "acid-base" system.

The instant novel acid-addition salt forms of the (N-substitutedsulfonamido) azo dyestuffs provide shades of yellow to blue-red. Theyhave valuable properties as water-soluble direct dyes useful in thedyeing art for coloring natural fibers, synthetic fiber-formingmaterials and cellulose materials such as threads, sheets, filaments,textile fabrics and the like as well as in the manufacture of paper,varnishes, inks, coatings and plastics. Further, the free base forms ofthe (N-substituted sulfonamido) azo dyestuffs including theN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido derivative are useful aspigments and as pigment additives.

The (N-substituted sulfonamido) azo dyestuffs and the water-solubleacid-addition salts thereof of this invention are characterized by goodlightfastness. The azo dyestuffs in the form of their water-solubleacid-addition salts are useful as dyes for dyeing operations, and in thewater-insoluble free base forms as well as their acid-addition saltforms as pigments for printing operations on woven and non-wovensubstrates made from natural fibers, such as wool, cellulose or linen,those made from semi-synthetic fibers, such as regenerated cellulose asrepresented by rayon or viscose, or those made from synthetic fibers,such as polyaddition, polycondensation or polymerization compounds. Suchdyeings or printings can be carried out in accordance with the usualdyeing and printing processes.

The (N-substituted sulfonamido) azo dyestuffs and their acid-additionsalt forms of this invention are also suitable for surface coloring orprinting paper products and cardboard as well as for coloring paperpulps. Moreover, they are useful for incorporation into lacquers andfilms of various constitutions, for example, those made from celluloseacetate, cellulose propionate, polyvinyl chloride, polyethylene,polypropylene, polyamides, polyesters of alkyd resins. In addition, thesubject compounds are suitable for coloring natural or synthetic resins,for example, acrylic resins, epoxy resins, polyester resins, vinylresins, polystyrene resins, or alkyd resins.

The (N-substituted sulfonamido) azo dyestuffs are readily converted tothe corresponding water-soluble dyes by treatment in an aqueous solutioncontaining from 0.5 to 10 equivalents of one or more of an inorganicacid, aliphatic or hydroxyaliphatic carboxylic acid and alkanesulfonicacid selected from the group consisting of hydrochloric, hydrobromic,acetic, propionic, glycolic, 3-hydroxypropionic, lactic, methanesulfonicand ethanesulfonic acids.

The acid-addition salt forms can be isolated from the aqueous solutionin which they are formed by techniques well known in the art, forexample, by salting out, precipitation or concentration by evaporation.However, the water-soluble dyes thus formed are readily utilized in theform of aqueous solutions for many of their applications, especially dordyeing cellulose. Accordingly, it is particularly preferred to retainthe dyes in a concentrated aqueous solution of the type regularlyemployed in the paper industry for dyeing paper products.

The acid-addition salt forms are especially valuable dyes for impartingstable yellow to blue-red shades to paper both sized and unsized. Foruse in the paper trade, the acid-addition salt forms of this inventionhave several outstanding advantages. Their high degree ofwater-solubility makes them particularly suitbale for the preparation ofliquid dye concentrates which are preferred in the paper industry. Theuse of concentrated aqueous solutions is particularly advantageous inview of the increasing trend toward automation, since these solutionsare conveniently handled and added to the pulp slurry in accuratelymeasured amounts by means of pump and meters. The subject aqueous dyeconcentrates are particularly suited to metered dyeing operationsbecause they have low viscosity which remains essentially unchanged overlong periods under ordinary storage conditions. Their low viscosityprovides another advantage in that they dissolve readily in the pulpslurry and prevent specking or blotching seen when more viscous dyeconcentrates are used. A further advantage of the concentrated aqueoussolutions is that of convenience in shipping and handling. In shippingand its use, the high degree of solubility of the acid-addition saltforms permit handling of solutions containing a higher dye content andresults in a desirable decrease in the weight and volume of solution peramount of dye. Furthermore, the concentrated aqueous dye solutions aremore convenient for the paper mills in that the handling of dry dye,with the concomitant dusting and caking problems associated withdissolving the dye prior to its addition to the pulp slurry areeliminated.

The subject dyes constituting my invention are generally less prone to"bleed" than dyes heretofore known when paper impregnated therewith iswet and placed in contact with moist white paper. This is a particularlydesirable property for dyes designed for coloring absorbent grades ofpaper used in facial tissues, napkins, paper towels and the like whereinit can be foreseen that the colored paper, wetted with common householdliquids such as water, soap and detergent solutions, milk, carbonatedand alcoholic beverages, vinegar, rubbing alcohol, and so forth, maycome in contact with other surfaces such as textiles, paper and the likewhich should be protected from stain. Another advantageous property ofthese new water-soluble dyes for use in the paper trade is found intheir high degree of color discharge when bleached with hypochlorite or"chlorine" bleach. This property of the acid-addition salt forms isparticularly desired by papermakers in order that dyed paper may becompletely bleached prior to reprocessing. Still another advantageousproperty of the water-soluble dyestuffs of this invention is found intheir high resistance to a change of shade when used to color cellulosicmaterials, which have either previously been treated with or are treatedsubsequent to dyeings, with wet-strength resin.

I have also found that the dyes of this invention have a high degree ofsubstantivity for bleached fiber such as is used in most coloreddisposable paper products. Moreover, they are absorbed by cellulosicfibers from aqueous solution at a very rapid rate. These properties areadvantageous to the paper industry, because it allows the dye to beadded to the pulp just prior to formation of the sheet.

The best mode contemplated by the inventor of carrying out thisinvention will now be described as to enable any person skilled in theart to which it pertains to make and use the same.

In accordance with one of its process aspects of this invention, the(N-substituted sulfonamido) disazo compounds according to Formulas I, IIand III are prepared by first preparing the appropriate (chlorosulfonylsubstituted) disazo compound by interacting the corresponding (sulfonicacid substituted) disazo compound with chlorosulfonic acid and thionylchloride and second, interacting the resulting (chlorosulfonylsubstituted) disazo compound with the appropriate amine of the formulaH₂ NR¹ to obtain the desired (R¹ N-sulfonamido substituted) disazocompound of Formulas I, II or III. By way of illustration, the disazocompound (4,4'-diaminodiphenyldisulfide→2 moles of2-hydroxy-6-naphthalenesulfonic acid is first interacted withchlorosulfonic acid and thionyl chloride. The reaction is convenientlycarried out in excess chlorosulfonic acid at a temperature in the rangeof 10° to 70° C. After the reaction mixture is cooled to ambienttemperature, it is poured onto ice to obtain the desired(chlorosulfonated) disazo compound. In the second step, the(chlorosulfonated) disazo compound is interacted with an excess of aminehaving the formula H₂ NR¹, for example, the N,N-dialkylalkylenediamine,3-dimethylaminopropylamine. This reaction is conveniently carried out inan aqueous medium in the presence of an alkaline carbonate, for example,potassium carbonate and an organic base, for example, pyridine at atemperature in the range of 20° to 85° C. After cooling to 35° to 45°C., the reaction mixture is adjusted to a pH of approximately 7.9 usingan inorganic acid, for example, hydrochloric acid and the desired(3-dimethylaminopropylsulfonamido) substituted disazo compound ofFormula I is isolated by filtration.

The disazo compounds of Formulas IV and V and the mixtures of monoazocompounds of Formula VII are conveniently obtained in accordance withanother of the process aspects of this invention. In general, the novelazo compounds of this invention can be prepared essentially the sameprocedure. The particular products obtained, that is the dyestuff ofFormulas IV, V or VII are dependent on the nature of the substituents ofthe starting amine as is discussed hereinbelow. Thus the appropriatediazotized (N-substituted sulfonamido)-R² -aniline is coupled with theappropriate coupling component, for example,4,4'-bi-acetoacet-o-toluidide orN,N-bis(3-hydroxy-2-naphthocarbonyl)diaminoethane. By way ofillustration, two molecular proportions of2-methoxy-5-N-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}aniline aredissolved in a dilute aqueous mineral acid, for example, hydrochloricacid and chilled by the addition of ice to a temperature in the range of0° to 15° C., preferably 0° to 5° C. and diazotized by the addition ofdilute aqueous solution of sodium nitrite. In a second container thecoupling component, for example, 4,4'-bi-acetacet-o-toluidide, isdissolved in a dilute alcohol-water solution of an inorganic base, forexample, sodium hydroxide or potassium hydroxide with heating ifnecessary, to complete solution. The coupling component solution isgradually added to the diazonium salt solution or alternatively thediazonium salt solution is gradually added to the coupling solution, butin either case, a temperature in the range of 15° to 20° C. ismaintained during the strike with the addition of ice to the reactionmixture. This reaction mixture is then stirred to complete the couplingand develop the color at a temperature in the range of 30° to 35° C.After the coupling is complete, the reaction mixture is adjusted to pH8.0-9.0 with the addition of an inorganic base, for example, sodiumhydroxide or potassium hydroxide and the alcohol is distilled from thereaction mixture. The resulting mixture is cooled by the addition of iceand the correspondingN-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}disazo compound ofFormula IV is isolated by filtration.

In accordance with a still another process aspect of the invention, thecompounds represented by Formula VI are prepared by dissolving the azocompound (sulfanilic acid→2-methoxyaniline) in a dilute aqueous mineralacid, for example, hydrochloric acid and chilled by the addition of iceto a temperature in the range of 10° to 25° C. and diazotizing the azocompound by the addition of dilute aqueous solution of sodium nitrite.In a second container the coupling component, for example,2-hydroxy-6-naphthalenesulfonic acid, is dissolved in a dilute solutionof an inorganic base, for example, sodium carbonate. The couplingsolution is then chilled to 0° to 10° C. by the addition of ice and thecold diazonium salt solution is then gradually added to the couplingsolution maintaining 0° to 10° C. and slight alkalinity by the additionof ice and sodium carbonate respectively. This reaction mixture isstirred to complete the coupling and develop the color at ambienttemperature. After the coupling is complete, the disazo disulfonic aciddisodium salt is isolated by filtration. In subsequent steps, the disazocompound containing two sulfonic acid moieties is then interacted withchlorosulfonic acid and thionyl chloride to obtain the chlorosulfonatedproduct which is further reacted with an excess of amine of the formulaH₂ NR¹, each of these steps being similar to those described above forthe compounds of Formula VI.

In accordance with yet another one of the process aspects of thisinvention, the N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R²-nitrobenzenes of Formula XI are prepared by interacting anitrobenzenesulfonyl chloride and 1-(2-aminoethyl)-2-imidazolidinone.The reaction is conveniently carried out in an organic base, forexample, pyridine at a temperature in the range of 85° to 95° C. Thereaction solution of N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R²-nitrobenzene is heated to remove a portion of the reaction medium byevaporation, cooled to ambient temperature and a dilute aqueous solutionof a mineral acid, for example, hydrochloric acid is added. Theresulting slurry is cooled to a temperature in the range of 0° to 5° C.and the substituted nitrobenzene of Formula XI collected by filtration.The product may be purified by recrystallization from any suitablesolvent, for example, ethyl alcohol.

In accordance with another one of the process aspects of this invention,the N-[2-(2-oxo-imidazolidin-1-yl)ethyl]-R² -sulfonamidoanilines ofFormula XI are prepared by reducing the correspondingN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R² -nitrobenzene. Thereduction is conveniently carried out in a dilute aqueous alcoholicsolution in the presence of an inorganic acid, for example, hydrochloricacid using the appropriate reducing agent, for example, powderedmetallic iron at the reflux temperature of the reaction medium. Theresulting reaction mixture is made slightly alkaline by the addition ofan alkaline carbonate, for example, sodium carbonate, treated withdecolorizing charcoal and clarified. The clarified solution isconcentrated by evaporation and the product of Formula XI is isolated byfiltration.

In accordance with a still further process aspect of the invention, theN-[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido-R² -anilines of Formula XIare prepared by hydrolyzing the correspondingN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R² -anilines. Thehydrolysis is conveniently carried out in a dilute aqueous acid, forexample, sulfuric acid at the reflux temperature. The hydrolysissolution is made slightly alkaline by the addition of concentratedammonium hydroxide and theN-[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido-R² -anilines of Formula XIare isolated by filtration.

In accordance with another of the process aspects of the invention, theN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R² -acetanilides ofFormula XI are prepared by interacting the appropriate acetamido-R²-benzenesulfonyl chloride and 1-(2-aminoethyl)-2-imidazolidinone. Thereaction is conveniently carried out in water in the presence of analkaline carbonate, for example, sodium carbonate and an organic base,for example, pyridine at a temperature in the range of 20° to 60° C. Theproduct is isolated by filtration.

The N-[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido-R² -anilines ofFormula XI are conveniently prepared by hydrolyzing the correspondingN-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido-R² -acetanilides in adilute aqueous acid. The hydrolysis solution is made slightly alkalineby the addition of concentrated ammonium hydroxide and theN-[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido-R² -anilines of Formula XIare isolated.

The generally known monoazo and disazo compound starting materials areidentified herein by the well known nomenclature shorthand,amine→coupling agent, for example, aniline→β-naphthol, which signifiesthe diazotized amine is coupled to the coupling agent.

The requisite monoazo and disazo compounds useful as starting materialsare known as a class in the art and are commercially available or can bereadily obtained by procedures well known in the prior art.

The requisite chlorosulfonyl-R² -nitrobenzenes and chlorosulfonyl-R²-acetanilides useful as starting materials are known as a class in theart and are commercially available or can be readily obtained byprocedure well known in the art.

The requisite 1-(2-aminoethyl)imidazolidinone intermediate is a knowncompound readily obtained by procedures taught in U.S. Pat. Nos.2,613,212 and 2,868,727. Thus, one molecular equivalent of urea isinteracted with one molecular equivalent of diethylene triamineliberating ammonia. The reaction can be carried out neat or in thepresence of water which is distilled off during the course of thereaction. The reaction is conveniently carried out at a temperature inthe range of 100° to 250° C. The 1-(2-aminoethyl)imidazolidinone can beused directly from the reaction or it can be distilled at reducedpressure before using.

The reactive amine intermediate required for interaction with the(chlorosulfonyl) disazo and monoazo compounds to obtain the compounds ofFormulas I, II, III, IV, V, VI and VII wherein R¹ isalkylene-N-non-tertiary-(C₁ to C₄ alkyl)₂ are known compounds whosepreparation is well-known in the prior art. The following compounds areexemplary of these reactive amine compounds useful in the practice ofthis invention.

3-Dimethylaminopropylamine,

3-Diethylaminopropylamine,

3-Dibutylaminopropylamine,

2-Dimethylaminoethylamine,

2-Diethylaminoethylamine,

2-Diisopropylaminoethylamine

and

4-Diethylaminobutylamine.

The following examples set forth the methods of preparation of the(N-substituted sulfonamido) disazo and monoazo compounds; acid-additionsalts thereof; and (N-substituted sulfonamido) substituted anilines,acetanilides and nitrobenzenes. Included in the following examples arethe results of the "bleed" tests as described in Example 1 of samples ofpaper prepared from pulp dyed with the products of the followingexamples. In these "bleed" tests the dyed sample of paper is wetted withthe appropriate household liquid and placed as a filler between clean,dry, white filter paper. After a period of time, the so-called"sandwich" is disassembled and the component piece mounted and dried.The filter papers are then examined under daylight and evaluated withrespect to the amount of dye which bled from the dyed paper sample tothe filter paper.

EXAMPLE 1

A. With stirring, 158.0 g of 1-(2-aminoethyl)-2-imidazolidinone and 63.6g of sodium carbonate were added to 200.0 ml of cold water and themixture stirred for approximately one and one half hours. Atapproximately 20° C., there was added to this mixture, 120.4 g of 97percent 4-acetamidobenzenesulfonyl chloride in small increments overapproximately fifteen minutes. Two milliliters of pyridine was addedbringing the pH to 9.6. After approximately forty-five minutes ofstirring at approximately 25° C., the pH had dropped to 9.3 and wasadjusted to 9.6 by the addition of 3.0 ml of 50 percent aqueous sodiumhydroxide. After stirring approxmately eighteen hours at ambienttemperature, the pH was 9.0. The addition of 4.0 ml of 50 percentaqueous caustic brought the pH to 9.5. The slurry was stirredapproximately one hour at 50° to 55° C. After cooling the slurry to roomtemperature, the solid was collected by filtration and washed with three250.0 ml portions of cold water. The yellow filter cake was added to1250.0 ml of warm water with stirring, and the slurry heated to andmaintained at 90° to 95° C. for approximately one and one half hours.The hot slurry was then filtered. The filtrate was set aside at 9° C.for four days. The residue was extracted a second time with 500.0 ml ofwater, at 95° to 98° C. for two hours, filtered without cooling anddried to obtain 17.0 g of an insoluble white solid. In the first waterextract, a pale yellow solid separated from solution. The solid wascollected by filtration and dried to obtain 107.5 g of4-N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamidoacetanilide (FormulaXI: ##STR21## R² =H; R⁶ =acetamido) which melted over the range 168° to173.5° C. The filtrate from the second water extraction was chilled at2° to 4° C. for approximately twenty-four hours and the yellow solidwhich formed was collected by filtration and dried in vacuo at 80° C. toobtain 3.7 g of a solid which melted at 173° to 174.5° C.

B. A mixture consisting of 72.0 ml of 37 percent hydrochloric acid, 40.0ml of water, 40.0 ml of glacial acetic acid and 65.3 g of4-N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamidoacetanilide obtained inpart A above, was heated with stirring at reflux temperature forapproximately thirty-one hours. After cooling to room temperature, thesolution was poured into 350.0 ml of water and with stirring 142.0 ml ofconcentrated ammonium hydroxide was added maintaining a pH of 8.0-8.5for approximately two hours. The pH was slowly adjusted to 7.0 by theaddition of 14.0 ml of 37 percent hydrochloric acid. The resultingsolution was evaporated to dryness with gentle heating. The residue wasadded to 400.0 ml of ethyl alcohol and refluxed for approximately onehour. Without cooling, the solid was collected by filtration, washed twotimes, each with 50.0 ml of portions of ethyl alcohol, and dried invacuo at 55° to 60° C. to obtain 35.4 g of4-N-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}aniline (Formula XI:R^(1') =4-C₂ H₄ NHC₂ H₄ NH₂ ; R² =H; R⁶ =NH₂) which melted over therange 218° to 225.5° C. The alcohol filtrate was cooled overnight atapproximately 9° C. and the solid which precipitated was collected byfiltration, washed two times, each with 25.0 ml of cold ethyl alcohol,and dried at 55° to 60° C. in vacuo to obtain 20.5 g of4-N-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}aniline which melted at223° and 225.5° C. This 20.5 g of product was added to 50.0 ml ofdistilled water and with stirring, 10.0 ml of concentrated hydrochloricacid and 1.0 g of decolorizing charcoal was added. After approximatelyfive minutes, the mixture was filtered. The clear filtrate was pouredinto 500.0 ml of isopropyl alcohol and the resulting slurry was placedin a refrigerator overnight. The solid was collected by filtration,washed with isopropanol and dried at 70° to 75° C. in vacuo to obtain16.1 g of trihydrochloride salt which melted at 238° to 242° C.

The nuclear magnetic resonance spectrum was concordant with the assignedstructure. Mass spectral analysis of the free base showed m/e peaks at228(M⁺ --C₂ H₄ NH₂) and 156(M⁺ --NHC₂ H₄ NHC₂ H₄ NH₂).

C. To a solution of 12.9 g of4-N-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}aniline obtained inpart A above in 100.0 ml of water and 25.0 ml of concentratedhydrochloric acid, there was added crushed ice to lower the temperatureto approximately 0° C. The amine was diazotized at a temperature in therange of 0° to 10° C. by adding 30.5 ml of a 10 percent aqueous sodiumnitrite solution. The reaction mixture was stirred at a temperature ofless than 10° C. for approximately 30 minutes after which time theexcess nitrite was removed by the gradual addition of sulfamic aciduntil the nitrite ion could no longer by detected by testing withstarch-iodide test paper. Sodium acetate was added slowly to the colddiazonium solution until slightly alkaline to Congo Red test paper and0.03 ml of nonylphenoxypoly(ethyleneoxy)ethanol (Igepol® CO-630) wasadded.

D. In a separate container, 12.2 g of 3-hydroxy-2-naphth-o-anisidide wasmixed with 100.0 ml of warm water, 50.0 ml of isopropyl alcohol and 6.0ml of 50 percent aqueous solution of sodium hydroxide.

E. The solution thus obtained in part D above was added in a thin streamto the diluted diazonium solution from part C above. When the additionwas complete, the mixture had a pH of 4.5 which remained approximatelyconstant after stirring overnight at ambient temperature. The resultantorange mixture was adjusted to pH 8.5 by the addition of concentratedammonium hydroxide and heated to 50° to 55° C. for approximately twohours. This mixture was heated at 75° to 85° C. for one half hour andfiltered. The filter cake was washed three times, each with 160.0 ml ofone percent aqueous sodium chloride solution, and air dried to obtain19.3 g of the orange dyestuff having the formula ##STR22## The orangesolid obtained above was added to a mixture of 200.0 ml of water, 40.0ml of glacial acetic acid and 20.0 ml of methyl alcohol and heated withstirring at reflux temperature for approximately one hour, cooledslightly and 2.0 g of diatomaceous earth was added and the heatingcontinued for approximately one half hour. The hot mixture was filteredand the filter cake washed with 75.0 ml of hot water. The clear orangefiltrate was added to 600.0 ml of isopropyl alcohol and the resultingmixture placed in a refrigerator overnight. In the morning the separatedsolid was collected by filtration, washed four times, each with 100.0 mlof cold isopropyl alcohol, and dried in a vacuum oven at 50° to 55° C.to obtain 4.7 g of acetic acid salt of the dyestuff.

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of dye per liter of solution showed amaximum at 500 millimicrons, A=0.753.

F. A concentrated dye solution was prepared by adding 2.39 g of thisdyestuff from part E above to a mixture of 8.0 ml of water, 3.2 g ofglacial acetic acid and 1.6 g of ethylene glycol. The mixture wasstirred until solution was complete. Paper dyed with aqueous dilutionsof this concentrate had a red-orange shade and was found to be highlybleachable in the bleach test described below. The dye was found tobleed moderately in the water bleed test and have an appreciable bleedin the soap and milk bleed tests when tested in accord with theprocedure described below.

DYEING PROCEDURE

A 0.1 percent stock dye solution was prepared by diluting 6.45 g of theconcentrated dye solution from part F above to a volume of one literwith distilled water. With stirring, 150.0 ml of the 0.1 percent dyesolution was added to 100.0 g of an aqueous slurry containingapproximately 3 grams of bleached kraft pulp (600 Canadian StandardFreeness). Agitation was continued for approximately fifteen minutesprior to dilution with water to a volume of four liters with agitation.The dyed pulp was then formed into an 8 by 8 inch square of paper bymeans of a filter-box. The paper sheet was pressed between two blottersand then dried at 180° F. for four minutes between two fresh dryblotters to yield a uniformly dyed red-orange paper sheet.

B. Sized Paper Grades:

With stirring, 150.0 ml of the 0.2 percent stock dye solution was addedto 100.0 g of an aqueous slurry containing 3 grams of bleached kraftpulp (600 Canadian Standard Freeness). After approximately three minutesof stirring, 5.0 g of a 1.5 percent water solution of papermaker's alumwas added. Stirring was continued for approximately fifteen minutesbefore it was diluted to four liters with water and the pH adjusted to5.0 with dilute sulfuric acid. The dyed fiber slurry was drawn into an 8by 8 inch square of paper and dried as described in part A above.

TESTING PROCEDURE

The following test procedures were employed to determine the resistanceof the dyestuffs to bleed in moist paper, to bleed from paper in thepresence of soap or milk, and to bleaching with hypochlorite bleach.

WATER "BLEED" TEST

This procedure is a modification of the AATCC Standard Test Method15-1962, "Colorfastness to Perspiration."

Test pieces consisting of four plies, each one inch square, are cut fromthe dyed paper to be tested. One or more dyed papers of known dyemigration quality are included in the test series as standards.

The absorbent material consists of filter paper having a relativelysmooth finish (Whatman #1, 4.25 cm. dia. equivalent). In addition,smooth, flat, glass or clear plastic plates of adequate stiffness,measuring two inches wide and three inches long, are required asseparating plates. A 1000 gram weight serves as a dead weight loading.

Four filter paper absorbent pieces are use for each dyed paper testsquare, two for each side.

The migration test "sandwich" is constructed as follows. A separatingplate is placed on a horizontal support and two pieces of the filterpaper placed centrally on this plate with the smoother side up. Thesquare dyed paper test pieces, held by tweezers, are immersed in tapwater at room temperature for five seconds, drained for five seconds,and immediately centered on the filter paper. Immediately, two pieces offilter paper are centered on the test square and followed at once byanother separating plate. This "sandwich" is pressed for a moment withthe fingers, after which, without delay, two pieces of filter paper arepositioned on the top separating plate as before to receive a secondtest square of wetted dyed paper. The above procedure is then repeatedas rapidly as possible and without interruption, stacking one "sandwich"on the other, until all dyed paper test pieces have been put under test.

As soon as a stack is completed, a 1000 gram weight is centered on thetop separating plate. The stack is allowed to stand at room temperature(75° F.) for fifteen minutes.

At the end of the migration period, the stack is disassembled, and eachdyed paper test square and its filter paper absorbents clipped to asupporting card. A separate card is used for each test square. The dyedpaper test squares and filter papers are air dried at room temperaturefor at least two hours (in the dark) before ranking. Relative degrees ofdye migration, as compared to that from standard samples, are determinedby visual ratings, in daylight, of the intensity of dye stain on thefilter paper surfaces which had been in contact with the test square.

The evaluations are graded on the basis of the following scale:

    ______________________________________                                        Bleed Grade     Definition                                                    ______________________________________                                        none            no observable bleed                                           trace           first noticeable bleed                                        slight          approximately twice the                                                       trace amount of dye bleed                                     moderate        approximately four times                                                      the trace amount of dye                                                       bleed                                                         appreciable     approximately eight times                                                     the trace amount of dye                                                       bleed                                                         much            approximately sixteen times                                                   the trace amount of dye                                                       bleed                                                         very much       approximately thirty-two                                                      times the trace amount                                                        of dye bleed                                                  ______________________________________                                    

SOAP BLEED TEST

This procedure utilizes the same method employed in the Water Bleed Testdescribed above, except that the dyed paper test squares are immersed ina 0.5 percent tap water solution of white soap flakes (a mixture of 80percent sodium soap and 20 percent potassium soap produced from 70percent tallow and 30 percent coconut oil glyceride blend; "Ivory"brand, Proctor and Gamble Co.) at 120° F., instead of water alone.

MILK BLEED TEST

This procedure utilizes the same method employed in the water bleed testdescribed above, except that the dyed paper squares are immersed in roomtemperature homogenized milk instead of water.

BLEACH TEST

This procedure compares the degree to which the color of dyed paperswould be discharged in a waste paper recovery operation employinghypochloric bleach.

A preliminary estimate of bleachability is obtained by placing a drop ofhypochlorite bleach, containing 2.5 percent available chlorine; on thedyed paper and allowing it to dry at room temperature. From this test,both rate and degree of bleachability are estimated.

A more accurate test, approximating paper mill procedure, is performedby defibering three grams of dyed paper in 150.0 ml of distilled waterusing a kitchen blender. The defibered pulp slurry is placed in a jarand hypochlorite is added to the extent desired, usually 2.5 percentavailable chlorine based on the weight of the dry fiber. The slurryconsisting of pulp and hypochlorite is adjusted to pH 9 with dilutesulfuric acid or dilute aqueous solution of sodium hydroxide and placedin a water bath to maintain the interval in the temperature range of115° F. and 125° F. After the test is started, the jar is looselycapped. At five minute intervals, the cap is tightened and the jarinverted twice to circulate the liquor. The cap is loosened betweeninversions. After twenty minutes, the pH is checked, and if higher than7.5, is adjusted thereto. The test is then continued for an additionaltwenty minutes (with five minutes between inversions). The terminal pHis generally found to be 6.0-6.5. An excess of sodium thiosulfate isadded as an antichlor, mixed for five minutes and the slurry is dilutedto a concentration of approximately 0.3 percent of fiber. Sheets arethen prepared at pH 7 without a washing step. Finally, this sheet ispressed and dried in a paper dryer. Control dyeings at specific levelscan then be made to accurately determine the loss of strength of coloron bleaching.

EXAMPLE 2

A. Following a procedure similar to that described in Example 1, partsC, D and E above, 12.9 g of4-N-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}aniline from Example 1,part B above was diazotized and coupled to 4.4 g of 2-hydroxynaphthaleneto obtain, after extraction with isopropyl alcohol, 6.0 g of an orangesolid having the formula ##STR23## The visible absorption spectrum of anaqueous acetic acid solution of this dyestuff, containing 0.02 g of dyeper liter of solution showed a maximum at 484 millimicrons, A=0.683.

B. A concentrated dye solution was prepared by adding 5.0 g of thedyestuff from part A directly above to a mixture of 10.0 ml of water,4.0 g of glacial acetic acid and 2.0 g of ethylene glycol. The mixturewas stirred until solution was complete. Paper dyed with aqueousdilutions of this concentration had an orange shade and was found to behighly bleachable in the bleach test described above. The dye was foundto bleed moderately in the water bleed test and to have much bleed inboth the milk and soap bleed tests when tested in accord with theprocedure described above.

EXAMPLE 3

A. To a solution of 160.0 ml of dry pyridine and 25.8 g of1-(2-aminoethyl)-2-imidazolidinone there was added 46.5 g ofm-nitrobenzenesulfonyl chloride in small increments over approximatelyone hour. The reaction mixture was heated and maintained at 87° to 93°C. for approximately one hour and slowly 100.0 ml of pyridine wasdistilled from the reaction mixture. After cooling, 400.0 ml of waterand 25.0 ml of concentrated hydrochloric acid were added with stirringto the reaction mixture. The resultant slurry was cooled toapproximately 5° C. by means of an external ice bath and the solid wascollected by filtration. The filter cake was suspended in 350.0 ml ofwater and stirred for approximately one hour. The solid was collected byfiltration, washed with water and dried in a vacuum oven at 90° to 95°C. to obtain 36.0 g of3-N-[2-(2-oxo-imidazolin-1-yl)ethyl]sulfonamidonitrobenzene (Formula XI:##STR24## R² =H; R⁶ =NO₂). The solid was added to 300.0 ml of ethylalcohol, heated at reflux for approximately one hour, cooled slightlyand filtered to remove and insolubles. The filtrate was cooled to roomtemperature and placed in a refrigerator overnight. The separated solidwas collected by filtration and dried in vacuo at 50° to 60° C. toobtain 28.0 g of purified product which melted over the range 117° to139° C.

B. A mixture of 19.0 g of finely powdered iron, 70.0 ml of water and 0.5ml of concentrated hydrochloric acid was heated at reflux forapproximately fifteen minutes and 250.0 ml of ethyl alcohol was addedslowly while maintaining reflux. The heat source was removed and 26.8 gof 3-N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamidonitrobenzene frompart A above was added in small increments at a rate sufficient tomaintain a gentle reflux. After the addition was complete, the mixturewas refluxed for an additional three hours. The reaction mixture wascooled slightly and 3.0 g of sodium carbonate and 2.0 g of decolorizingcharcoal were added and reflux temperature was maintained for anadditional thirty minutes. Without cooling the reaction mixture wasclarified by filtering through a diatomaceous earth coated filter andthe residue washed with 50.0 ml of ethyl alcohol. The filtrate wasconcentrated by evaporation and the solid which formed was collected byfiltration, washed with 35.0 ml of ethyl alcohol and dried in vacuo at50° to 55° C. to obtain 20.0 g of3-N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamidoaniline (Formula XI:##STR25## R² =H; R⁶ =NH₂) which melted over the range of 168° to 174° C.Seventeen grams of this product was slurried in 100.0 ml of water,filtered and dried to obtain 16.3 g of purified product.

C. With stirring, a mixture of 13.0 ml of water, 4.7 g of concentratedsulfuric acid and 4.26 g of3-N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamidoaniline obtained inpart B above was heated at reflux for approximately 38 hours duringwhich time carbon dioxide was evolved. After cooling, concentratedammonium hydroxide was added slowly to the reaction mixture until it wasalkaline to Brilliant Yellow test paper. The resulting mixture wasplaced in a refrigerator overnight. The solid which formed was collectedby filtration, washed with 10.0 ml of cold water and dried to obtain0.89 g of the starting aniline. A thin layer chromatographic analysis ofthe filtrate disclosed that3-N-[N'-(2-aminoethyl)-2-aminoethyl]sulfonamidoaniline (Formula XI:R^(1') =3-NHC₂ H₄ NHC₂ H₄ NH₂ ; R² =H; R⁶ =NH₂) was the major productpresent.

D. Proceeding in a manner similar to that described in Example 1, partsC, D and E above, 29.4 ml of the solution from part C directly abovecontaining predominantly3-N-[N'-2-aminoethyl)-2-aminoethyl]sulfonamidoaniline was diazotized andthe diazonium salt coupled to 2.93 g of 3-hydroxy-2-naphth-o-anisided toobtain 21.0 g of a water wet filter cake of the dyestuff having theformula ##STR26## With stirring, the water wet filter cake was mixedwith 10.0 ml of a glacial acetic acid and 2.0 g of urea. The resultingsolution was filtered to remove trace amounts of insolubles.

The visible absorption spectrum of an aqueous dilution containing theacetic acid addition salt of the dyestuff solution showed a maximum at495 millimicrons.

EXAMPLE 4

A. To 180.0 g of chlorosulfonic acid, 42.5 g of o-methoxyacetanilide wasadded slowly while maintaining 25° to 30° C. by means of an ice-waterbath. The reaction mixture was stirred approximately twelve hours andthen was added slowly to a mixture of ice and water keeping thetemperature under 15° C. The solid which formed was collected byfiltration and washed almost neutral to Congo Red test paper with coldwater. The filter cake was added slowly to a mixture consisting of 200.0ml of cold water, 47.8 g of 1-(2-aminoethyl)-2-imidazolidinone, 37.6 gof potassium carbonate and 1.0 ml of pyridine while maintainingapproximately 30° C. by means of an external ice-water bath. Theresulting mixture was stirred overnight at ambient temperature. Theresulting slurry was heated gradually during two hours to 65° C. andmaintained at approximately 65° C. for ninety minutes. After cooling,the solid was collected by filtration, washed with cold water and driedin a vacuum oven at 50° to 55° C. to obtain 58.6 g of2-methoxy-5-N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamidoacetanilide(Formula XI: ##STR27## R² =2-OCH₃ ; R⁶ =acetamido) which melted over therange 163° to 167° C.

B. With stirring, 50.8 g of the mixture containing2-methoxy-5-N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamidoacetanilidefrom part A above, was added slowly to a solution of 35.0 ml ofconcentrated sulfuric acid dissolved in 186.0 ml of water. The resultingmixture was heated at reflux temperature for approximately five hours,16.0 ml of concentrated sulfuric acid was added and the reflux wasmaintained for an additional 19 hours. After cooling, the resultingsolution was added slowly to 2000.0 ml of isopropyl alcohol withstirring. The resulting mixture was set aside in the refrigeratorovernight. The separated solid was collected by filtration, washed withone liter of isopropyl alcohol and dried in a vacuum oven at 75° to 80°C. to obtain 73.2 g of sulfuric acid addition salt of2-methoxy-5-N-{[N'-(2-aminoethyl)-2-amino-ethyl]sulfonamido}aniline(Formula XI: R^(1') =5-NHC₂ H₄ NHC₂ H₄ NH₂ ; R² =2-OCH₃ ; R⁶ =NH.sub. 2)which melted over the range of 91° to 104° C.

C. Following a procedure similar to that described in Example 1, partsC, D and E above, 34.0 g of sulfuric acid addition salt2-methoxy-5-N-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}aniline frompart B directly above, was diazotized and the resulting diazonium saltcoupled to 19.5 g of 3-hydroxy-2-naphth-o-anisidide to obtain 36.5 g ofthe monoazo compound having the formula ##STR28## as a red-coloredsolid.

The visible absorption spectrum of an aqueous acetic acid solutioncontaining 0.02 g of dyestuff per liter of solution showed a maximum at410 millimicrons, A=0.417.

EXAMPLE 5

A. To a solution of 34.0 g of the sulfuric acid addition salt of2-methoxy-5-N-{[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido}aniline,prepared in a manner similar to that described in Example 4, part Babove, in 100.0 ml of water, was added 12.0 ml of concentratedhydrochloric acid and 200.0 g of crushed ice. The amine was diazotizedat a temperature between 0° to 5° C. by slowly adding a solution of 4.9of sodium nitrite dissolved in 31.0 ml of water. The reaction mixturewas stirred for one hour at a temperature in the range of 0° to 5° C.after which time the excess nitrite was removed by the gradual additionof sulfamic acid until the nitrite ion could no longer by detected onstarch-iodide test paper. Slowly, sodium acetate was added to the colddiazonium solution until the solution tested neutral to Congo Red testpaper.

B. In a separate container, 13.2 g of 4,4'-bi-acetoaceto-toluidide, 28.0ml of isopropyl alcohol, 133.0 ml of warm water and 4.2 ml of 50 percentaqueous sodium hydroxide were stirred until a solution resulted.

C. The solution of the coupling component from part B directly above wasadded in a thin stream to the cold diazonium solution from part A above.The reaction mixture was stirred at a temperature in the range of 15° to20° C. approximately two hours and stirring continued at 30° to 35° C.until there was no diazonium salt remaining. The pH was adjusted from3.5 to 8.5 by the addition of 50 percent sodium hydroxide. The resultingslurry was heated, distilling off isopropyl alcohol until thetemperature of 102° C. was reached and approximately 60.0 ml ofdistillate was collected. The slurry was cooled and the solid collectedby filtration, washed with water and dried in a vacuum oven at 50° to55° C. to obtain 28.9 g of disazo compound having the formula ##STR29##a yellow-colored solid.

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of dye per liter of solution showed amaximum at 401 millimicrons, A=0.716.

D. The 28.9 g of solids from part C above was added to a mixture of100.0 ml of water and 10.0 ml of glacial acetic acid and stirred atambient temperature for approximately six hours. The volume of thesolution was adjusted to 825.0 ml with water, heated to approximately75° C., cooled and allowed to stand overnight at room temperature. Thesolution was filtered to remove a trace of insoluble matter. Withstirring, the filtrate was adjusted to pH 8.5-9.0 with the slow additionof 50 percent aqueous sodium hydroxide and the resulting mixture heatedat 75° to 80° C. for approximately one hour and cooled to ambienttemperature. The solid which separated was collected by filtration andwashed with a small amount of cold water. The wet cake was dissolved in15.0 ml of glacial acetic acid and 10.0 ml of water.

Paper dyed with aqueous dilutions of this concentrate had a green-yellowshade and was found to be 93 percent bleachable in the bleach testdescribed hereinabove. The dye was found to exhibit no bleed in thewater, soap or milk bleed tests described hereinabove.

E. With stirring, 3.0 g of the dyestuff from the same starting materialsprepared in a manner similar to that described in part C above, wasadded slowly to 75.0 ml of distilled water and 3.0 ml of concentratedhydrochloric acid was added. The mixture was heated to 60° to 70° C. anda gel-like solution formed. An additional 3.0 ml of concentratedhydrochloric acid was added to the gel. With stirring, the gel was addedto 400.0 ml of isopropyl alcohol and stirring continued for one hour.The resulting solid was collected by filtration, washed with isopropylalcohol and dried. The dried solid was dissolved in a mixture of 100.0ml of water and 10.0 ml of ethylene glycol with heating. After filteringthe cloudy solution to remove a trace of insolubles, the filtrateobtained was added to 450.0 ml of isopropyl alcohol. Upon standingovernight, the solid which formed was collected by filtration, washedwith isopropyl alcohol and dried in vacuo to obtain 2.6 g of thehydrochloride salt of the dyestuff indicated in part C above.

The visible absorption spectrum of an aqueous solution of thishydrochloride salt of this dyestuff, containing 0.02 g of the salt perliter of solution showed a maximum at 404 millimicrons, A=0.838.

EXAMPLE 6

A. With stirring, 152.0 g of water wet filter cake containing3-acetamido-4-methoxybenzenesulfonyl chloride, prepared as described inExample 4, part A above, was added slowly to a mixture consisting of200.0 ml of water, 37.8 g of dimethylaminopropylamine, 27.6 g ofpotassium carbonate and 1.0 ml of pyridine while maintaining atemperature in the range of 30° to 35° C. by means of an externalice-water bath. After stirring overnight at ambient temperature, theseparated solid was collected by filtration, washed with 100.0 ml of 5percent aqueous sodium chloride solution and 100.0 ml of ice water. Thecake was dried in a vacuum oven at 55° C. to obtain 65.9 g of2-methoxy-5-(dimethylaminopropylsulfonamido)acetanilide (Formula XI:R^(1') =5-SO₂ NHC₃ H₆ N(CH₃)₂ ; R² =2-OCH₃ ; R⁶ =acetamido), a solid,which melted over the range 144° to 148° C.

B. A mixture consisting of 150.0 ml of water, 40.0 ml of concentratedhydrochloric acid and 33.0 g of2-methoxy-5-(dimethylaminopropylsulfonamido)acetanilide obtained in partA above, was heated at reflux with stirring for approximately two hours.The resulting solution was cooled and allowed to stand overnight atambient temperature. In the morning 300.0 g of crushed ice was added andthe amine was diazotized at a temperature in the range of 0° to 5° C. byadding a solution of 7.0 g of sodium nitrite dissolved in 44.0 ml ofwater. The reaction mixture was stirred for one hour at less than 5° C.after which the excess nitrite was removed by the gradual addition ofsulfamic acid until the nitrite ion could no longer by detected bytesting with starch-iodide test paper. The cold solution was madeslightly alkaline to Congo Red test paper by the addition of sodiumacetate.

C. In a separate container 18.9 g of 4,4"-bi-acetoaceto-toluidide wasmixed with 190.0 ml of warm water, 40.0 ml of isopropyl alcohol and 6.0ml of 50 percent aqueous sodium hydroxide. The solution thus obtainedwas added in a thin stream to the cold diazonium solution obtained inpart B above. The reaction mixture, pH 4.5, was stirred at 15° to 20° C.until consumption of the diazonium salt was complete. The mixture waswarmed to approximately 35° C. and adjusted with 50 percent causticuntil alkaline to Brilliant Yellow test paper. The slurry was heated to50° C. and the solid was collected by filtration and washed with water.The water wet filter cake was suspended in two liters of water andsodium carbonate was added until the slurry was alkaline to BrilliantYellow test paper. The slurry was maintained in the temperature range of80° to 95° C. for approximately ninety minutes, cooled and the solidcollected by filtration, washed with water and dried in vacuo to obtain45.0 g of a disazo compound having the formula ##STR30## as ayellow-colored solid.

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of dye per liter of solution showed amaximum at 403 millimicrons, A=1.154.

Paper dyed with dilute acetic acid solutions of this dyestuff had agreen-yellow shade and was found to be 100 percent bleachable in thebleach test described hereinabove. The dye was found not to bleed in thewater and milk bleed tests and to bleed slightly in the soap bleed testdescribed hereinabove.

D. With stirring, a mixture of 3.0 g of the dyestuff from part C aboveand 50.0 ml of 2-ethoxy-1-ethanol was heated at reflux for approximatelyone hour. After cooling to ambient temperature, the solid was collectedby filtration, washed with 25.0 ml of 2-ethoxy-1-ethanol and dried invacuo at 50° C. The dried solid was added to 100.0 ml of distilledwater, heated to 50° C. and 10.0 ml of glycolic acid was added. Theresultant mixture was stirred at 70° C. for approximately ninetyminutes, cooled and poured into 300.0 ml of acetone. The yellowprecipitate which formed was collected by filtration. Theacetone-water-wet solid was added to 100.0 ml of distilled water withstirring and was heated to 70° C. for approximately one hour. Theresulting solution was filtered to remove a trace of insolubles and theclear filtrate added to 300.0 ml of acetone. The yellow precipitate wascollected by filtration and dried at 50° C. to obtain the glycolic acidaddition salt of the dyestuff.

EXAMPLE 7

A. Proceeding in a manner similar to that described in Example 6, part Aabove, a water-wet filter cake containing 58.2 g of3-acetamido-4-methoxybenzenesulfonyl chloride was interacted with 59.3 gof dibutylaminopropylamine in a solution consisting of 200.0 ml ofwater, 23.7 g of potassium carbonate and 1.0 ml of pyridine at ambienttemperature overnight. The solid which formed was collected byfiltration, washed with 1.5 liters of ice cold water and dried in avacuum oven at 40° C. to obtain 76.2 g of2-methoxy-5-(dibutylaminopropyl)sulfonamidoacetanilide (Formula XI: R¹'=5--SO₂ NH--C₃ H₆ N(C₄ H₉)₂ ; R² =2--OCH₃ ; R⁶ =acetamido) which meltedover the range 59° to 64° C.

B. Following the procedures described in Example 6, parts B and C above,41.4 g of 2-methoxy-5-(dibutylaminopropyl)sulfonamidoacetanilide frompart A directly above was hydrolyzed to obtain the hydrochloride saltsolution of the amine. The amine hydrochloride was diazotized and theresulting diazonium salt was coupled to 18.9 g of4,4'-bi-acetacet-o-toluidide. The separated dyestuff was collected byfiltration, washed with water until the filtrate was free of alkali whentested with Brilliant Yellow test paper and dried in vacuo at atemperature in the range of 90° to 100° C. to obtain 55.5 g of a disazocompound having the formula ##STR31##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of dye per liter of solution showed amaximum at 400 millimicrons, A=0.981.

Paper dyed with a dilute acetic acid solution of this dyestuff had ayellow shade and was found to be highly bleachable in the bleach testdescribed hereinabove. The dye was found not to bleed in the water andmilk bleed tests and to bleed only slight in the soap bleed testdescribed hereinabove.

EXAMPLE 8

With stirring, 22.5 g of the pigment4,4'-diaminodiphenyldisulfide→1-hydroxynapthalene-4-sulfonic acid wasadded gradually to 200.0 g of chlorosulfonic acid while maintaining atemperature in the range of 20° to 25° C. by means of an externalice-water bath. The resulting mixture was heated gradually toapproximately 60° C. and stirred one hour at approximately 60° C.Slowly, over approximately thirty minutes, 11.6 ml of thionyl chloridewas added to the mixture while maintaining a temperature in the range of53° to 60° C. The reaction mixture was stirred approximately 20 hours atapproximately 60° C. After cooling to 20° C., the reaction mixture wasadded slowly with stirring to a mixture of 300.0 g ice, 300.0 ml ofwater and 25.0 g of sodium chloride maintaining a temperature below 10°C. by the gradual addition of an additional 500.0 g of ice. Afterstirring the resulting slurry for approximately thirty minutes at atemperature in the range of 0° to 10° C., the solid was collected byfiltration and washed with two liters of two percent aqueous sodiumchloride solution to obtain 97.4 g of water-wet filter cake containingthe disazo compound having the formula ##STR32##

B. At a temperature in the range of 20° to 25° C., 48.7 g of thewater-wet filter cake from part A directly above, was added withstirring to a mixture of 70.0 ml of water and 7.7 g ofdimethylaminopropylamine. After stirring approximately three hours atambient temperature, the reaction mixture was heated to a temperature inthe range of 75° to 80° C. and maintained in this range forapproximately two hours. After cooling the reaction slurry toapproximately 40° C., the pH was adjusted to 7.9 with the addition ofthree normal aqueous hydrochloric acid. The solid was collected byfiltration, washed with water and dried to obtain 8.8 g of the disazocompound having the formula ##STR33## as a dark red solid, which meltedover the range 220° to 230° C. with decomposition.

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of dye per liter of solution showed amaximum at 505 millimicrons, A=0.480.

Paper dyed with a dilute acetic acid solution of this dyestuff had ablue-red shade and was found to be highly bleachable in the bleach testdescribed hereinabove. The dye was found not to bleed in the water bleedtest and to bleed only slightly in the milk bleed test describedhereinabove.

EXAMPLE 9

A. Following a procedure similar to that described in Example 8, part Aabove, 22.0 g of the pigment4,4'-diaminodiphenyldisulfide→2-hydroxynaphthalene-6-sulfonic acid wasinteracted with 5.8 ml of thionyl chloride in chlorosulfonic acid toobtain 79.5 g of water-wet filter cake containing the disazo compoundhaving the formula ##STR34##

B. Proceeding in a manner similar to that described in Example 8, part Babove, 39.75 g of the water-wet pulp from part A directly above wasinteracted with 7.7 g of dimethylaminopropylamine to obtain 10.3 g ofthe disazo compound having the formula ##STR35##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.025 g of dye per liter of solution showed amaximum at 484 millimicrons, A=0.906.

Paper dyed with a dilute acetic acid solution of this dyestuff had ayellow-red shade and was found to be highly bleachable in the bleachtest described hereinabove. The dye was found to have a trace of bleedin the water bleed test described hereinabove.

EXAMPLE 10

A. In a manner similar to that described in Example 8, part A above,24.0 g of the pigment,4,4'-diaminodiphenyldisulfide→2-hydroxynaphthalene-3,6-disulfonic acidwas interacted with 11.6 ml of thionyl chloride in chlorosulfonic acidto obtain 77.4 g of water-wet filter cake containing the disazo compoundhaving the formula ##STR36##

B. Following a procedure similar to that described in Example 8, part Babove, 38.7 g of the water-wet filter cake from part A directly abovewas interacted with 15.4 g of dimethylaminopropylamine to obtain 18.9 gof the disazo compound having the formula ##STR37##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of the dye per liter of solution showeda maximum at 496 millimicrons, A=0.348.

Paper dyed with a dilute acetic acid solution of this dyestuff had ayellow-red shade and was found to be highly bleachable in the bleachtest described hereinabove. The dye was found to have a slight bleed inthe water bleed test described hereinabove.

EXAMPLE 11

A. Proceeding in a manner similar to that described in Example 6, part Babove, 14.2 g of 2-methoxy-5-(dimethylaminopropylsulfonamido)acetanilidewas hydrolyzed to obtain the hydrochloride salt solution of the amine.This amine hydrochloride salt was diazotized by the addition of 3.0 g ofsodium nitrite dissolved in 20.0 ml of water to form the diazonium salt.

B. A solution consisting of 8.4 g ofN,N'-bis(3-hydroxy-2-naphthocarbonyl)diaminoethane, 80.0 ml of warmwater, 20.0 ml of isopropanol and 4.5 ml of 50 percent aqueous sodiumhydroxide was stirred approximately one hour and filtered to remove atrace of insoluble matter. To the filtrate, 140.0 ml of cold water wasadded and immediately the cold diazonium salt solution from part A abovewas added at such a rate as to maintain a temperature in the range of10° to 15° C. The reaction mixture was stirred at a temperature in therange of 10° to 15° C. until the comsumption of the diazonium salt wascomplete. The pH of the slurry was adjusted to 8.0 by the addition of 50percent aqueous sodium hydroxide and the metallic green-colored solidwas collected by filtration, washed with water and dried to obtain 12.4g of the disazo compound having the formula ##STR38##

The visible absorption spectrum of an aqueous acetic acid solution ofthe dyestuff, containing 0.02 g of the dye per liter of solution showeda maximum at 502 millimicrons, A=0.506.

Paper dyed with a dilute acetic acid solution of this dyestuff had ayellow-red shade and was found to be highly bleachable in the bleachtest described hereinabove. The dye was found to bleed slightly when inthe water bleed test described hereinabove.

EXAMPLE 12

A. A solution consisting of 15.35 g of the azo dyestuff (sulfanilicacid→2-methoxyaniline), 260.5 ml of water and 5.0 g of sodiumbicarbonate at 75° C. was added rapidly to a mixture of 220.0 g ofcrushed ice, 60.0 ml of water and 42.0 ml of concentrated hydrochloricacid to obtain a gelatinous mixture. While maintaining a temperature inthe range of 17° to 21° C., 4.2 g of sodium nitrite dissolved in 10.0 mlof water was added slowly to the gelatinous mixture over approximatelyfifteen minutes. The reaction mixture was stirred at approximately 25°C. for two hours with excess nitrite, after which the excess nitrite wasremoved by the gradual addition of sulfamic acid until nitrite ion couldno longer be detected by testing with starch-iodide test paper and themixture was cooled to 10° C.

In a separate container, 37.2 g of 2-hydroxy-6-naphthalene sulfonic acidwas dissolved in 450.0 ml of water and 175.0 ml of 15.4 percent aqueoussodium carbonate solution and 300.0 g of ice were added. Slowly,approximately 300.0 ml of the cold diazonium solution obtained above wasadded in a thin stream while maintaining 10° C. An additional 175.0 mlof 15.4 percent aqueous sodium carbonate was added and the remainingdiazonium solution was added keeping the temperature under 10° C. Theresulting pH was 8.0. After stirring overnight at ambient temperature,there was added to the solution, 225.0 g of sodium chloride and stirringcontinued. The solid which separated was collected by filtration, washedwith approximately 900.0 ml of 20 percent aqueous sodium chloridesolution and dried in vacuo at 65° C. to obtain 47.4 g of the disazocompound having the formula ##STR39##

B. With stirring, 47.4 g of the red solid obtained in part A above, wasadded to 200.0 g of chlorosulfonic acid over approximately one hourwhile maintaining a temperature in the range of 20° to 25° C. Afterstirring the resulting mixture for approximately ninety minutes, 11.5 mlof thionyl chloride was added dropwise and this mixture was stirredovernight at room temperature. The reaction mixture was added slowly toa mixture of 300.0 ml of water, 300.0 ml of ice and 25.0 g of sodiumchloride maintaining a temperature below 10° C. with the gradualaddition of 600.0 g of ice. After the addition was complete, theresulting slurry was stirred 20-30 minutes, 25.0 ml of xylene was added,and stirring continued for 20 minutes. The solid was collected byfiltration and washed with 200.0 ml of 2 percent aqueous sodium chloridesolution. The filter cake was resuspended in 700.0 ml of 2 percentaqueous sodium chloride solution and stirred for approximately tenminutes at a temperature less than 10° C. The solid was collected byfiltration from the suspension to obtain 92.1 g of the water-wet filtercake containing the chlorosulfonyl derivative of the dyestuff indicatedin part A above.

C. To a mixture of 70.0 ml of water and 30.6 g of3-dimethylaminopropylamine, slowly 92.1 g of the water-wet filter cakefrom part B above was added while maintaining 20° to 25° C. Theresulting slurry was stirred overnight at ambient temperature. Afterdiluting the slurry with 100.0 ml of water, it was heated toapproximately 60° C., stirred approximately thirty minutes and the pHadjusted to 8.5 by the addition of 50.0 ml of 3 normal hydrochloricacid. The solid was collected by filtration and washed with 500.0 ml ofhot water. The water-wet filter cake was resuspended in 500.0 ml of hotwater and stirred at approximately 40° C. for approximately fortyminutes, the solid collected by filtration, washed with hot water anddried in vacuo to obtain 99.9 g of the disazo compound having theformula ##STR40##

The visible absorption spectrum of an aqueous acetic acid solution ofthis dyestuff, containing 0.02 g of dye per liter of solution showed amaximum at 531 millimicrons, A=1.068. Paper dyed with a dilute aceticacid solution of this dyestuff had a violet-red shade and was found tobe highly bleachable in the bleach test described above. The dye wasfound to bleed slightly from paper in the water bleed test describedabove.

What is claimed is:
 1. A disazo compound bearing (N-substitutedsulfonamido) groups said disazo compound selected from the groupconsisting of ##STR41## in which R¹ represents a moiety selected fromthe group consisting of alkylene-NH-alkylene-NH₂,alkylene-N-(non-tertiary C₁ to C₁₄ alkyl)₂, ##STR42## in which alkylenerepresents --CH₂ CH₂ -- and --CH₂ CH₂ CH₂ --,R², R³, and R⁴ representhydrogen, C₁ -C₃ alkyl or C₁ -C₃ alkoxy; or the acid-addition salt formsof said disazo compounds.
 2. A disazo compound according to claim 1 ofthe formula ##STR43## in which R¹ has the same respective meanings givenin claim
 1. 3. The disazo compound, according to claim 2 wherein, R¹ is--(CH₂)₃ N(CH₃)₂.
 4. A disazo compound, according to claim 1, of theformula ##STR44## in which R¹ has the same respective meanings given inclaim
 1. 5. The disazo compound, according to claim 4 wherein, R¹ is--(CH₂)₃ N(CH₃)₂.
 6. The disazo compound, according to claim 4 wherein,R¹ is ##STR45##
 7. A disazo compound, according to claim 1, of theformula ##STR46## in which R¹ has the same respective meanings given inclaim
 1. 8. The disazo compound, according to claim 7 wherein, R¹ is--(CH₂)₃ N(CH₃)₂.
 9. A disazo compound, according to claim 1, of theformula ##STR47## in which R^(1'), R² and R⁴ each have the samerespective meanings given in claim
 1. 10. The disazo compound, accordingto claim 9 wherein, R¹ is --(CH₂)₃ N(CH₃)₂, R² is methoxy and R⁴ ismethyl.
 11. The disazo compound, according to claim 9 wherein, R¹ is--(CH₂)₂ H(CH₂)₂ NH₂, R² is methoxy and R⁴ is methyl.
 12. The disazocompound, according to claim 9 wherein, R¹ is --(CH₂)₃ N(C₄ H₉)₂, R² ismethoxy and R⁴ is methyl.
 13. A disazo compound, according to claim 1,of the formula ##STR48## in which R¹ and R² each have the samerespective meanings given in claim
 1. 14. The disazo compound, accordingto claim 13 wherein, R¹ is --(CH₂)₃ N(CH₃)₂ and R² is methoxy.
 15. Adisazo compound, according to claim 1, of the formula ##STR49## in whichR¹ and R³ each have the same respective meanings given in claim
 1. 16.The disazo compound, according to claim 15 wherein, R¹ is --(CH₂)₃N(CH₃)₂ and R³ is methoxy.
 17. A process for preparing a (N-substituted)sulfonamido disazo compound according to claim 1 which comprises in thefirst step interacting poly(sulfonic acid) substituted disazo compoundwith chlorosulfonic acid and thionyl chloride to obtain a(chlorosulfonyl) substituted disazo compound and in a second step,interacting a (chlorosulfonyl) substituted disazo compound obtained instep one with an amine of the formula H₂ NR¹ to obtain a (N-substitutedsulfonamido) substituted disazo compound wherein R¹ has the samerespective meanings given in relation to claim
 1. 18. A process forpreparing a (N-substituted sulfonamido) disazo compound according toclaim 1 which comprises in a first step diazotizing the appropriate(N-substituted sulfonamido)-R² -aniline and in a second step couplingtwo molecular proportions of the diazotized aniline with one molecularproportion of a coupling component wherein R¹ and R² each have the samerespective meanings given in claim
 1. 19. A process for preparing(N-substituted sulfonamido) disazo compound according to claim 15 whichcomprises in a first step diazotizing a known azo compound(aminobenzenesulfonic acid→R³ -aniline) and coupling the diazonium saltwith approximately one molecular proportion of a coupling component, a2-hydroxynaphthalenesulfonic acid; in a second step interacting thedisazo dyestuff thus formed with chlorosulfonic acid and thionylchloride; in a third step interacting the resultingpoly(chlorosulfonated) disazo compound with an excess of an amine of theformula H₂ NR¹ ; and in a fourth step isolating the resulting poly(R¹-sulfonamido) disazo compound.